EP3861976A1 - Matériaux dentaires à base d'agents de réticulation cyclopolymérisables - Google Patents
Matériaux dentaires à base d'agents de réticulation cyclopolymérisables Download PDFInfo
- Publication number
- EP3861976A1 EP3861976A1 EP20155585.1A EP20155585A EP3861976A1 EP 3861976 A1 EP3861976 A1 EP 3861976A1 EP 20155585 A EP20155585 A EP 20155585A EP 3861976 A1 EP3861976 A1 EP 3861976A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- weight
- hydrocarbon radical
- material according
- dental material
- sub
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 239000005548 dental material Substances 0.000 title claims abstract description 29
- 239000003431 cross linking reagent Substances 0.000 title 1
- 150000001875 compounds Chemical class 0.000 claims abstract description 34
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 30
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 28
- 125000003118 aryl group Chemical group 0.000 claims abstract description 13
- 125000004430 oxygen atom Chemical group O* 0.000 claims abstract description 13
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims abstract description 6
- 125000004185 ester group Chemical group 0.000 claims abstract description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N urethane group Chemical group NC(=O)OCC JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 3
- 125000004434 sulfur atom Chemical group 0.000 claims abstract description 3
- 239000000178 monomer Substances 0.000 claims description 78
- 239000000203 mixture Substances 0.000 claims description 38
- 239000000945 filler Substances 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 23
- -1 di- Chemical compound 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 13
- UEKHZPDUBLCUHN-UHFFFAOYSA-N 2-[[3,5,5-trimethyl-6-[2-(2-methylprop-2-enoyloxy)ethoxycarbonylamino]hexyl]carbamoyloxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC(=O)NCCC(C)CC(C)(C)CNC(=O)OCCOC(=O)C(C)=C UEKHZPDUBLCUHN-UHFFFAOYSA-N 0.000 claims description 12
- 229920006395 saturated elastomer Polymers 0.000 claims description 12
- 239000003999 initiator Substances 0.000 claims description 10
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 10
- 150000001252 acrylic acid derivatives Chemical class 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 8
- 238000011049 filling Methods 0.000 claims description 8
- 238000010526 radical polymerization reaction Methods 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- AMFGWXWBFGVCKG-UHFFFAOYSA-N Panavia opaque Chemical compound C1=CC(OCC(O)COC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OCC(O)COC(=O)C(C)=C)C=C1 AMFGWXWBFGVCKG-UHFFFAOYSA-N 0.000 claims description 6
- 125000004122 cyclic group Chemical group 0.000 claims description 6
- 239000003479 dental cement Substances 0.000 claims description 6
- LRZPQLZONWIQOJ-UHFFFAOYSA-N 10-(2-methylprop-2-enoyloxy)decyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCCCCCOC(=O)C(C)=C LRZPQLZONWIQOJ-UHFFFAOYSA-N 0.000 claims description 5
- HWSSEYVMGDIFMH-UHFFFAOYSA-N 2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOC(=O)C(C)=C HWSSEYVMGDIFMH-UHFFFAOYSA-N 0.000 claims description 4
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 claims description 4
- NMXWWAMBELVUOS-UHFFFAOYSA-N [2-(2-methylprop-2-enoyloxymethyl)-1-tricyclo[5.2.1.02,6]decanyl]methyl 2-methylprop-2-enoate Chemical compound C12CCCC2(COC(=O)C(C)=C)C2(COC(=O)C(=C)C)CC1CC2 NMXWWAMBELVUOS-UHFFFAOYSA-N 0.000 claims description 4
- QUZSUMLPWDHKCJ-UHFFFAOYSA-N bisphenol A dimethacrylate Chemical compound C1=CC(OC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OC(=O)C(C)=C)C=C1 QUZSUMLPWDHKCJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012966 redox initiator Substances 0.000 claims description 4
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- 230000008439 repair process Effects 0.000 claims description 3
- ZDQNWDNMNKSMHI-UHFFFAOYSA-N 1-[2-(2-prop-2-enoyloxypropoxy)propoxy]propan-2-yl prop-2-enoate Chemical compound C=CC(=O)OC(C)COC(C)COCC(C)OC(=O)C=C ZDQNWDNMNKSMHI-UHFFFAOYSA-N 0.000 claims description 2
- VOBUAPTXJKMNCT-UHFFFAOYSA-N 1-prop-2-enoyloxyhexyl prop-2-enoate Chemical compound CCCCCC(OC(=O)C=C)OC(=O)C=C VOBUAPTXJKMNCT-UHFFFAOYSA-N 0.000 claims description 2
- HYQASEVIBPSPMK-UHFFFAOYSA-N 12-(2-methylprop-2-enoyloxy)dodecyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCCCCCCCCCOC(=O)C(C)=C HYQASEVIBPSPMK-UHFFFAOYSA-N 0.000 claims description 2
- NEBBLNDVSSWJLL-UHFFFAOYSA-N 2,3-bis(2-methylprop-2-enoyloxy)propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC(OC(=O)C(C)=C)COC(=O)C(C)=C NEBBLNDVSSWJLL-UHFFFAOYSA-N 0.000 claims description 2
- LTHJXDSHSVNJKG-UHFFFAOYSA-N 2-[2-[2-[2-(2-methylprop-2-enoyloxy)ethoxy]ethoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOCCOCCOCCOC(=O)C(C)=C LTHJXDSHSVNJKG-UHFFFAOYSA-N 0.000 claims description 2
- NGFFKUHICVFZTR-UHFFFAOYSA-N 2-[2-[4-[2-[4-[2-(2-methylprop-2-enoyloxy)ethoxy]phenyl]propan-2-yl]phenoxy]ethoxy]ethyl 2-methylprop-2-enoate Chemical compound C1=CC(OCCOCCOC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(OCCOC(=O)C(C)=C)C=C1 NGFFKUHICVFZTR-UHFFFAOYSA-N 0.000 claims description 2
- DXNINXCZCMZEOY-UHFFFAOYSA-N 2-[4-[2-[4-[1-(2-methylprop-2-enoyloxy)propan-2-yloxy]phenyl]propan-2-yl]phenoxy]propyl 2-methylprop-2-enoate Chemical compound C1=CC(OC(COC(=O)C(C)=C)C)=CC=C1C(C)(C)C1=CC=C(OC(C)COC(=O)C(C)=C)C=C1 DXNINXCZCMZEOY-UHFFFAOYSA-N 0.000 claims description 2
- LIEMOMJIUYRBNE-UHFFFAOYSA-N 2-methylprop-2-enoic acid;1-[4-(2-phenylpropan-2-yl)phenoxy]ethane-1,2-diol Chemical compound CC(=C)C(O)=O.C=1C=C(OC(O)CO)C=CC=1C(C)(C)C1=CC=CC=C1 LIEMOMJIUYRBNE-UHFFFAOYSA-N 0.000 claims description 2
- XOJWAAUYNWGQAU-UHFFFAOYSA-N 4-(2-methylprop-2-enoyloxy)butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCCCOC(=O)C(C)=C XOJWAAUYNWGQAU-UHFFFAOYSA-N 0.000 claims description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 2
- IAXXETNIOYFMLW-COPLHBTASA-N [(1s,3s,4s)-4,7,7-trimethyl-3-bicyclo[2.2.1]heptanyl] 2-methylprop-2-enoate Chemical compound C1C[C@]2(C)[C@@H](OC(=O)C(=C)C)C[C@H]1C2(C)C IAXXETNIOYFMLW-COPLHBTASA-N 0.000 claims description 2
- AMUNHMVMESMYQL-UHFFFAOYSA-N [2-hydroxy-3-[4-[2-[4-[2-hydroxy-3-(2-methylprop-2-enoyloxy)propyl]phenyl]propan-2-yl]phenyl]propyl] 2-methylprop-2-enoate Chemical compound C1=CC(CC(O)COC(=O)C(=C)C)=CC=C1C(C)(C)C1=CC=C(CC(O)COC(=O)C(C)=C)C=C1 AMUNHMVMESMYQL-UHFFFAOYSA-N 0.000 claims description 2
- FHLPGTXWCFQMIU-UHFFFAOYSA-N [4-[2-(4-prop-2-enoyloxyphenyl)propan-2-yl]phenyl] prop-2-enoate Chemical class C=1C=C(OC(=O)C=C)C=CC=1C(C)(C)C1=CC=C(OC(=O)C=C)C=C1 FHLPGTXWCFQMIU-UHFFFAOYSA-N 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 125000004386 diacrylate group Chemical group 0.000 claims description 2
- 239000011256 inorganic filler Substances 0.000 claims description 2
- 229910003475 inorganic filler Inorganic materials 0.000 claims description 2
- 229940119545 isobornyl methacrylate Drugs 0.000 claims description 2
- CDOSHBSSFJOMGT-UHFFFAOYSA-N linalool Chemical compound CC(C)=CCCC(C)(O)C=C CDOSHBSSFJOMGT-UHFFFAOYSA-N 0.000 claims description 2
- 229940113115 polyethylene glycol 200 Drugs 0.000 claims description 2
- 230000001225 therapeutic effect Effects 0.000 claims description 2
- IQQVCMQJDJSRFU-UHFFFAOYSA-N 2-ethyl-2-(hydroxymethyl)propane-1,3-diol;prop-2-enoic acid Chemical compound OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.OC(=O)C=C.CCC(CO)(CO)CO IQQVCMQJDJSRFU-UHFFFAOYSA-N 0.000 claims 1
- 125000001931 aliphatic group Chemical group 0.000 claims 1
- 239000004557 technical material Substances 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 description 28
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 24
- 239000002245 particle Substances 0.000 description 23
- VVPQDZSFOPUXCX-UHFFFAOYSA-N C=C(CC(CC(C(OCCCCCCOC(C(CC(CC(C(O)=O)=C)(C(O)=O)C(O)=O)=C)=O)=O)=C)(C(O)=O)C(O)=O)C(O)=O Chemical compound C=C(CC(CC(C(OCCCCCCOC(C(CC(CC(C(O)=O)=C)(C(O)=O)C(O)=O)=C)=O)=O)=C)(C(O)=O)C(O)=O)C(O)=O VVPQDZSFOPUXCX-UHFFFAOYSA-N 0.000 description 21
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 16
- SYSQUGFVNFXIIT-UHFFFAOYSA-N n-[4-(1,3-benzoxazol-2-yl)phenyl]-4-nitrobenzenesulfonamide Chemical class C1=CC([N+](=O)[O-])=CC=C1S(=O)(=O)NC1=CC=C(C=2OC3=CC=CC=C3N=2)C=C1 SYSQUGFVNFXIIT-UHFFFAOYSA-N 0.000 description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000012071 phase Substances 0.000 description 11
- 230000009257 reactivity Effects 0.000 description 11
- 229910004298 SiO 2 Inorganic materials 0.000 description 10
- 238000007334 copolymerization reaction Methods 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 230000008602 contraction Effects 0.000 description 8
- 239000000499 gel Substances 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 8
- 238000005160 1H NMR spectroscopy Methods 0.000 description 7
- OXBLVCZKDOZZOJ-UHFFFAOYSA-N 2,3-Dihydrothiophene Chemical compound C1CC=CS1 OXBLVCZKDOZZOJ-UHFFFAOYSA-N 0.000 description 7
- 230000008901 benefit Effects 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000012043 crude product Substances 0.000 description 7
- 239000012074 organic phase Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical group CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 6
- 238000004440 column chromatography Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- KIMKGBGMXUPKJT-UHFFFAOYSA-N [diethyl-(4-methoxybenzoyl)germyl]-(4-methoxyphenyl)methanone Chemical compound C=1C=C(OC)C=CC=1C(=O)[Ge](CC)(CC)C(=O)C1=CC=C(OC)C=C1 KIMKGBGMXUPKJT-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 4
- 150000003926 acrylamides Chemical class 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000004132 cross linking Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 4
- 150000002978 peroxides Chemical class 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 125000001424 substituent group Chemical group 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 3
- IPOVOSHRRIJKBR-UHFFFAOYSA-N 2-ethylpropanedioyl dichloride Chemical compound CCC(C(Cl)=O)C(Cl)=O IPOVOSHRRIJKBR-UHFFFAOYSA-N 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 3
- 229910010413 TiO 2 Inorganic materials 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000012230 colorless oil Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
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- 238000009472 formulation Methods 0.000 description 3
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- 229910052760 oxygen Inorganic materials 0.000 description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 3
- 239000012312 sodium hydride Substances 0.000 description 3
- 229910000104 sodium hydride Inorganic materials 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- BVQVLAIMHVDZEL-UHFFFAOYSA-N 1-phenyl-1,2-propanedione Chemical compound CC(=O)C(=O)C1=CC=CC=C1 BVQVLAIMHVDZEL-UHFFFAOYSA-N 0.000 description 2
- KWVGIHKZDCUPEU-UHFFFAOYSA-N 2,2-dimethoxy-2-phenylacetophenone Chemical compound C=1C=CC=CC=1C(OC)(OC)C(=O)C1=CC=CC=C1 KWVGIHKZDCUPEU-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
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- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
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- 125000004429 atom Chemical group 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
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- KPXRGIVPSXFJEX-UHFFFAOYSA-N ethyl 2-(chloromethyl)prop-2-enoate Chemical compound CCOC(=O)C(=C)CCl KPXRGIVPSXFJEX-UHFFFAOYSA-N 0.000 description 2
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- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 2
- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical compound [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 description 2
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- 235000017557 sodium bicarbonate Nutrition 0.000 description 2
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- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 2
- 150000003573 thiols Chemical class 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- FIXNOXLJNSSSLJ-UHFFFAOYSA-N ytterbium(III) oxide Inorganic materials O=[Yb]O[Yb]=O FIXNOXLJNSSSLJ-UHFFFAOYSA-N 0.000 description 2
- XASAPYQVQBKMIN-UHFFFAOYSA-K ytterbium(iii) fluoride Chemical compound F[Yb](F)F XASAPYQVQBKMIN-UHFFFAOYSA-K 0.000 description 2
- QNODIIQQMGDSEF-UHFFFAOYSA-N (1-hydroxycyclohexyl)-phenylmethanone Chemical compound C=1C=CC=CC=1C(=O)C1(O)CCCCC1 QNODIIQQMGDSEF-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2602/00—Systems containing two condensed rings
- C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
- C07C2602/48—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing ten carbon atoms
Definitions
- the invention relates to radically polymerizable compositions which are particularly suitable as dental materials, such as, for example, cements, filling composites, veneering materials and materials for the production of inlays, onlays, crowns and bridges.
- the compositions contain a cyclopolymerizable crosslinker of the formula I and are notable for a low polymerization shrinkage.
- the polymerization of vinyl compounds or (meth) acrylates is known to lead to a significant volume contraction, since during the formation of the polymer chains per chain growth step, one double bond and one van der Waals bond are converted into two single bonds for each monomer molecule, i.e. the monomer units in the polymer chain move closer together compared to the monomer phase.
- the polymerization shrinkage can lead to disadvantageous shrinkage stresses, to the formation of gaps or reduced substrate adhesion and to impairment of the dimensional stability of moldings.
- the change in density during the polymerization is largely dependent on the molar mass and molar volume of the monomers. Higher molecular weight monomers show a lower volume contraction compared to monomers with a lower molar mass.
- cyclic monomers Compared to linear monomers, the volume contraction in the ring-opening polymerization of cyclic monomers is significantly lower, because in this case one covalent bond is opened and one covalent bond is opened per growth step is formed. Accordingly, cyclic monomers have found great interest as low-shrinkage matrix systems. However, cyclic monomers such as spiroorthocarbonates, cyclic ketene acetals or vinylcyclopropanes are significantly more expensive compared to methacrylates and in some cases have only a limited shelf life.
- the crosslinking thiol-ene polyaddition is distinguished from the radical polymerization of multifunctional methacrylates by an almost complete double bond conversion and a significantly lower polymerization shrinkage.
- the volume contraction per polymerized (meth) acrylate double bond is approx. 22-23 cm 3 / mol, while in the thiol-ene reaction the volume contraction is only 12-15 cm 3 per mole converted double bond.
- the crosslinking thiol-ene polyaddition proceeds according to a step growth mechanism and therefore has a significantly longer pregging phase compared to dimethacrylate polymerization, which also leads to a reduction in the polymerization contraction stress.
- the use of thiol-ene resins is limited by the very unpleasant odor of the thiols, the inherent flexibility of the thiol-ene polymers and the limited storage stability of the thiol-ene resins.
- cyclopolymerizable monomers have also been mentioned. These are di- or higher-functional monomers, the polymerization of which, due to their special monomer structure, takes place in addition to the intermolecular chain growth reaction, with the formation of 5- or 6-membered rings (see overview: D. Pasini, D Takeuchi, Chem. Rev. 118 (2016) 8993-9057 ). Cyclopolymerization was first described by Butler in 1957 for quaternary diallylammonium salts. Further examples of simple cyclopolymerizable monomers are acrylic and methacrylic anhydride, methyl allyl maleate and fumarate, diallyl phthalate and diethylene glycol bisallyl carbonate.
- U.S. 5,145,374 and the U.S. 5,380,901 disclose dental adhesives and composites which contain cyclopolymerizable bisacrylates (I) or oligomers (II).
- the materials should have a low polymerization shrinkage.
- the EP 3 335 688 A1 discloses dental materials containing cyclopolymerizable monomers such as 1,6-diene-2-carboxylic acid (ester) and 1,5-diene-2-carboxylic acid (ester) monomers. Specifically, ⁇ -allyloxymethacrylic acid cyclohexyl ester and methyl- ⁇ -allyloxymethyl methacrylate are mentioned.
- the materials should have a flowability suitable for dental purposes before hardening and a high mechanical strength after hardening, which is attributed to the ring formation during the cyclopolymerization.
- the WO 2014/040729 A1 discloses dental materials which contain N-allyl-substituted (meth) acrylamides, such as, for example, N, N, -di (allylacrylamido) propane.
- N-allyl-substituted (meth) acrylamides should be distinguished by high hydrolytic stability, good copolymerizability with conventional (meth) acrylates, low viscosity and excellent biocompatibility.
- the WO 2018/109041 A1 discloses dental materials which contain N-allyl-substituted (meth) acrylamides with phosphoric acid ester groups, such as, for example, N-acryl-8-allylaminooctylphosphoric acid ester.
- the (meth) acrylamides are said to be distinguished from 10-methyacryloyloxydecyl dihydrogen phosphate by a high chemical purity and a high heat of polymerization. In addition, they should give advantageous mechanical properties after curing.
- the invention is based on the object of providing dental materials which are characterized by low polymerization shrinkage, good mechanical properties and high reactivity in free-radical polymerization, in particular in photopolymerization.
- the substituents which may be present in the radicals R 1 to R 4 are preferably selected from chlorine, hydroxy and methoxy, the radicals optionally being substituted by 1 to 3 substituents.
- the radicals R 1 to R 4 are preferably not substituted by acidic groups and are particularly preferably unsubstituted.
- the formula I extends only to those compounds that are compatible with the chemical valence theory.
- the indication that a radical is interrupted, for example, by one or more O atoms, is to be understood as meaning that these atoms or groups are each inserted into the carbon chain of the radical. These atoms or groups are therefore limited on both sides by carbon atoms and cannot be terminal.
- C 1 radicals can be uninterrupted, branched or cyclic.
- aromatic hydrocarbon radicals are also understood to mean those radicals which contain aromatic and non-aromatic groups.
- a preferred aromatic radical is, for example, the diphenylpropane radical.
- the groups X, Y and Z can be identical or different.
- X and Y preferably have the same meaning; compounds in which X, Y and Z are identical are particularly preferred.
- the preferred, particularly preferred and very particularly preferred definitions given for the individual variables can each be selected independently of one another.
- Compounds in which all variables have the preferred, particularly preferred and very particularly preferred definitions are of course particularly suitable according to the invention.
- hydrocarbon radicals are preferably saturated hydrocarbon radicals. This applies both to the general definition and to the preferred and, in particular, also to the particularly preferred compounds of the formula I.
- Particularly preferred compounds of the formula Ia are the following substances:
- a preferred compound of the formula Ib is:
- the compounds of the formula I according to the invention contain four or six polymerizable groups and have crosslinking properties. They are distinguished by a high reactivity of the cyclopolymerizable groups in free-radical polymerization and are readily copolymerizable with conventional dental monomers, in particular with di (meth) acrylates. Because of their high reactivity, in contrast to the known, cyclopolymerizable N, N-disubstituted methacrylamides, they can also be homopolymerized, for example. In the homo- and copolymerization of the compounds of the formula I according to the invention, polymer networks with good mechanical properties are obtained which are advantageous for dental applications.
- the compounds of the formula I according to the invention are distinguished by a reduced polymerization shrinkage stress and a low polymerization shrinkage as a result of the cyclopolymerization. They thus make it possible to use these advantages for dental applications without impairing other properties that are also essential for dental purposes, such as in particular the mechanical properties.
- the compounds of the formula I are particularly suitable for the production of dental materials, for example for the production of coating or veneering materials, dental cements and, in particular, of filling composites. They are also suitable for the production of materials for the production or repair of dental prostheses, inlays, onlays, crowns or bridges. But they are also suitable for the production of radically polymerizable materials and thermosets for other purposes.
- the (dental) materials according to the invention preferably contain 0.5 to 70% by weight, particularly preferably 1 to 60% by weight and very particularly preferably 3 to 50% by weight of at least one compound of the formula I, based on the total mass of the material.
- the compounds of the formula I according to the invention are preferably used in combination with one or more polymerizable, mono- or multifunctional monomers (comonomers).
- Monofunctional monomers are understood as meaning compounds with one, and multifunctional monomers compounds with two or more, preferably 2 to 4, free-radically polymerizable groups.
- Preferred comonomers are radically polymerizable monomers.
- dental materials are preferred which contain at least one mono- or multifunctional (meth) acrylate as the radically polymerizable comonomer.
- Materials that are to be cured intraorally contain preferably mono- and / or multifunctional methacrylates as the free-radically polymerizable monomer. Methacrylates are therefore particularly preferred as comonomers. It has surprisingly been found that the compounds of the formula I according to the invention are readily copolymerizable with conventional (meth) acrylates.
- Preferred multifunctional methacrylates are dimethacrylates, in particular bisphenol A dimethacrylate, 2,2-bis [4- (2-hydroxy-3-methacryloyloxypropyl) phenyl] propane (Bis-GMA; an addition product of methacrylic acid and bisphenol A diglycidyl ether), ethoxy- or propoxylated bisphenol-A-dimethacrylate, such as 2- [4- (2-methacryloyloxyethoxyethoxy) phenyl] -2- [4- (2-methacryloyloxyethoxy) phenyl] propane) (SR-348c; contains 3 ethoxy groups), 2 , 2-bis [4- (2-methacryloyloxypropoxy) phenyl] propane, 1,6-bis [2-methacryloyloxy-ethoxycarbonylamino] -2,2,4-trimethylhexane (UDMA; an addition product of 2-hydroxyethyl methacrylate and 2, 2,4
- Multifunctional monomers in particular methacrylates, are preferably used in a total amount of at most 70% by weight, particularly preferably 1.5 to 60% by weight and very particularly preferably 2 to 50% by weight, based on the total mass of the material .
- Monofunctional monomers preferred according to the invention are monomethacrylates.
- Particularly preferred monomethacrylates are benzyl, tetrahydrofurfuryl, isobornyl methacrylate, p-cumyl-phenoxyethylene glycol methacrylate (CMP-1E), 2- (2-biphenyloxy) -ethyl methacrylate and mixtures thereof.
- Monofunctional monomers in particular methacrylates, are preferably used in an amount of a maximum of 10% by weight, particularly preferably 0 to 10% by weight and very particularly preferably 0 to 5% by weight, based on the total mass of the material.
- mono- and multifunctional acrylates are also suitable as comonomers.
- Preferred multifunctional acrylates are ethylene glycol diacrylate, hexanediol diacrylate, tripropylene glycol diacrylate, ethoxylated bisphenol A diacrylate, polyethylene glycol 200 diacrylate, trimethylol propane triacrylate, pentaerythritol tetraacrylate and mixtures thereof.
- Mono- and multifunctional acrylates are preferably used in an amount of a maximum of 50% by weight, preferably 0 to 50% by weight and particularly preferably 0 to 30% by weight, based on the total mass of the dental material.
- the total amount of comonomers is preferably a maximum of 70% by weight, particularly preferably 1.5 to 60% by weight and very particularly preferably 2 to 50% by weight, based on the total mass of the material.
- compositions according to the invention preferably contain an initiator for radical polymerization, e.g. for polymerization by UV light, by visible light, a thermal initiator and / or a redox initiator.
- an initiator for radical polymerization e.g. for polymerization by UV light, by visible light, a thermal initiator and / or a redox initiator.
- Photoinitiators are particularly preferred, and photoinitiators which are activated by visible light are very particularly preferred.
- Norrish type I initiators such as benzil dimethyl ketal, benzoin ethers, hydroxyphenyl ketones, dialkoxyacetophenones, benzoylcyclohexanol, trimethylbenzoylphosphine oxide and morpholinophenylaminoketones
- Preferred Norrish type II UV initiators are mixtures of, for example, benzophenone or thioxanthone derivatives with H donors such as alcohols, or thiols or electron donors such as amines.
- Preferred bimolecular photoinitiators for the visible range are ⁇ -diketones and its derivatives, such as 9,10-phenanthrenequinone, 1-phenyl-propane-1,2-dione, diacetyl or 4,4'-dichlorobenzil, and mixtures thereof.
- Camphorquinone (CC) and 2,2-dimethoxy-2-phenyl-acetophenone are particularly preferred, and ⁇ -diketones in combination with amines as reducing agents, such as ethyl 4- (dimethylamino) benzoate (EDMAB), N, N-dimethylaminoethyl methacrylate, N, N-dimethyl-sym.-xylidine or triethanolamine.
- EDMAB dimethylamino benzoate
- Preferred Norrish Type I photoinitiators for the visible range are bisacylphosphine oxides.
- Mixtures of the various photoinitiators can also be used advantageously, such as bis (4-methoxybenzoyl) diethylgerman or tetrakis (o-methyl-benzoyl) german in combination with camphorquinone and ethyl 4-dimethylaminobenzoate.
- Preferred thermal initiators are azo compounds such as 2,2'-azobis (isobutyronitrile) (AIBN), azobis (4-cyanovaleric acid) or peroxides, such as dibenzoyl peroxide, dilauroyl peroxide, tert-butyl peroctoate, tert-butyl perbenzoate or di- ( tert- butyl) peroxide.
- azo compounds such as 2,2'-azobis (isobutyronitrile) (AIBN), azobis (4-cyanovaleric acid) or peroxides, such as dibenzoyl peroxide, dilauroyl peroxide, tert-butyl peroctoate, tert-butyl perbenzoate or di- ( tert- butyl) peroxide.
- peroxides such as dibenzoyl peroxide, dilauroyl peroxide, tert-butyl peroctoate, tert-but
- Preferred combinations are combinations of dibenzoyl peroxide with an amine, preferably an N, N-dialkyl-substituted aromatic amine, which is substituted in the p-position, such as N, N-dimethyl-p-toluidine, N, N-dihydroxyethyl-p-toluidine, p -Dimethylamino benzoic acid ethyl ester.
- an amine preferably an N, N-dialkyl-substituted aromatic amine, which is substituted in the p-position, such as N, N-dimethyl-p-toluidine, N, N-dihydroxyethyl-p-toluidine, p -Dimethylamino benzoic acid ethyl ester.
- Combinations of a photoinitiator with a thermal or preferably a redox initiator are suitable for dual curing.
- Preferred redox initiators for dual curing are systems that contain a peroxide and a reducing agent, such as ascorbic acid, a barbiturate or a sulfinic acid, or a hydroperoxide in combination with a reducing agent and possibly catalytic amounts of metal ions, such as a mixture of cumene hydroperoxide, a thiourea derivative and copper (II) acetylacetonate.
- a peroxide and a reducing agent such as ascorbic acid, a barbiturate or a sulfinic acid
- a hydroperoxide in combination with a reducing agent and possibly catalytic amounts of metal ions, such as a mixture of cumene hydroperoxide, a thiourea derivative and copper (II) acetylacetonate.
- compositions according to the invention can advantageously also contain one or more organic or, preferably, inorganic fillers. Fibrous and, in particular, particulate fillers are preferred. Filler-containing compositions are particularly suitable as dental luting cements or filling composites.
- Fibers, carbon fibers, ceramic and aramid fibers and nanofibers or whiskers are preferred as fibrous fillers.
- Fibrous fillers are particularly suitable for the production of composite materials.
- Nanofibers are understood to mean fibers with a length of less than 100 nm and whiskers are understood to be needle-shaped single crystals, preferably made of aluminum oxide or silicon carbide. Whiskers typically have a diameter of a few ⁇ m and a length of up to 1 mm.
- Preferred particulate fillers are oxides such as SiO 2 , ZrO 2 and TiO 2 or mixed oxides of SiO 2 , ZrO 2 , ZnO and / or TiO 2 , nanoparticulate or microfine fillers such as fumed silica or precipitated silica, glass powder such as quartz, glass ceramic , Borosilicate or X-ray opaque glass powder, preferably barium or strontium aluminum silicate glasses, and X-ray opaque fillers such as ytterbium trifluoride, tantalum (V) oxide, barium sulfate or mixed oxides of SiO 2 with ytterbium (III) oxide or tantalum (V) oxide.
- oxides such as SiO 2 , ZrO 2 and TiO 2 or mixed oxides of SiO 2 , ZrO 2 , ZnO and / or TiO 2
- nanoparticulate or microfine fillers such as fumed silica or precipitated silica
- glass powder such as quartz, glass
- the oxides preferably have a particle size of 0.010 to 15 ⁇ m, the nanoparticulate or microfine fillers a particle size of 10 to 300 nm, the glass powder a particle size of 0.01 to 15 ⁇ m, preferably 0.2 to 1.5 ⁇ m, and the Radiopaque fillers have a particle size of 0.2 to 5 ⁇ m.
- Particularly preferred fillers are mixed oxides of SiO 2 and ZrO 2 , with a particle size of 10 to 300 nm, glass powder with a particle size of 0.2 to 1.5 ⁇ m, in particular X-ray opaque glass powder of, for example, barium or strontium aluminum silicate glasses, and X-ray opaque fillers with a Particle size from 0.2 to 5 ⁇ m, in particular ytterbium trifluoride and / or mixed oxides of SiO 2 with ytterbium (III) oxide.
- all particle sizes are weight-average particle sizes (D50 values), the particle size determination in the range from 0.1 ⁇ m to 1000 ⁇ m preferably being carried out using static light scattering, for example with a static laser scattering particle size analyzer LA- 960 (Horiba, Japan).
- a laser diode with a wavelength of 655 nm and an LED with a wavelength of 405 nm are used as light sources.
- the use of two light sources with different wavelengths enables the entire particle size distribution of a sample to be measured in just one Measurement run, with the measurement being carried out as a wet measurement. For this purpose, a 0.1 to 0.5% aqueous dispersion of the filler is produced and its scattered light is measured in a flow cell.
- the scattered light analysis for calculating the particle size and particle size distribution is carried out according to the Mie theory according to DIN / ISO 13320.
- the measurement of the particle size in the range from 5 nm to 0.1 ⁇ m is preferably carried out by dynamic light scattering (DLS) of aqueous particle dispersions, preferably with a He-Ne laser with a wavelength of 633 nm, at a scattering angle of 90 ° and at 25 ° C., for example with a Malvern Zetasizer Nano ZS (Malvern Instruments, Malvern UK).
- DLS dynamic light scattering
- Particle sizes smaller than 0.1 ⁇ m can also be determined using SEM or TEM images.
- Transmission electron microscopy (TEM) is preferably performed with a Philips CM30 TEM at an acceleration voltage of 300 kV.
- drops of the particle dispersion are applied to a 50 ⁇ thick copper grid (mesh size 300 mesh) that is coated with carbon, and the solvent is then evaporated. The particles are counted and the arithmetic mean is calculated.
- the fillers are divided into macro-fillers and micro-fillers according to their particle size, fillers with an average particle size of 0.2 to 15 ⁇ m being called macro-fillers and fillers with an average particle size of approx. 5 to 100 nm being called micro-fillers.
- Macro fillers are obtained, for example, by grinding quartz, X-ray opaque glasses, borosilicates or ceramics and usually consist of splinter-shaped parts.
- Micro-fillers such as mixed oxides can e.g. be produced by hydrolytic co-condensation of metal alkoxides.
- the fillers are preferably surface-modified.
- SiO 2 -based fillers are preferably surface-modified with methacrylate-functionalized silanes, particularly preferably with 3-methacryloyloxypropyltrimethoxysilane.
- Functionalized acidic phosphates such as 10-methacryloyloxydecyl dihydrogen phosphate can also be used to modify the surface of non-silicate fillers, for example ZrO 2 or TiO 2.
- the dental materials according to the invention can contain one or more other additives, especially stabilizers, colorants, microbiocidal active ingredients, additives that release fluoride ions, propellants, optical brighteners, plasticizers and / or UV absorbers.
- additives especially stabilizers, colorants, microbiocidal active ingredients, additives that release fluoride ions, propellants, optical brighteners, plasticizers and / or UV absorbers.
- Filling composites preferably have a filler content of 50 to 85% by weight, particularly preferably 70 to 80% by weight, and dental cements of 10 to 70% by weight, particularly preferably 60 to 70% by weight.
- Dental materials which consist of the components mentioned are particularly preferred, the individual components preferably each being selected from the preferred and particularly preferred substances mentioned above.
- compositions according to the invention are particularly suitable as dental materials, in particular as dental cements, filling composites and veneering materials and as materials for producing prostheses, artificial teeth, inlays, onlays, crowns and bridges.
- the compositions are primarily suitable for intraoral use by the dentist for the restoration of damaged teeth, i.e. for therapeutic use, e.g. as dental cements, filling composites and veneering materials.
- they can also be used non-therapeutically (extraorally), for example in the production or repair of dental restorations, such as prostheses, artificial teeth, inlays, onlays, crowns and bridges.
- compositions according to the invention are also suitable for the production of molded bodies for dental but also for non-dental purposes, which can be produced, for example, by means of casting, pressing and, in particular, by generative processes such as 3D printing.
- the invention also relates to the use of a compound according to formula I for the production of a free-radically polymerizable material, preferably a medical-technical and in particular a dental-medical material.
- 1,6-Hexanediol (42.3 mmol, 5.00 g) was dissolved in dry dichloromethane (DCM, 150 ml) and the apparatus was flushed with argon. The solution was cooled in ice water, then pyridine (105.8 mmol, 8.37 g) and then ethylmalonyl chloride (105.8 mmol, 15.93 g) were added first. The solution was stirred at room temperature for 4 h and then quenched with 1N HCl (150 ml). The aqueous phase was extracted 3 times with DCM (150 ml), the combined organic phases were washed with saturated NaHCO 3 solution (150 ml) and dried over anhydrous Na 2 SO 4.
- DCM dry dichloromethane
- the aqueous phase was extracted 3 times with diethyl ether (100 ml) and the combined organic phases were dried over anhydrous sodium sulfate. After evaporation of the solvent, the crude product was purified by means of column chromatography (PE: EE 4: 1) and the pure product was obtained as a viscous liquid in a yield of 21.95 g (77% of theory).
- Example 5 The volume contraction during the polymerization (polymerization shrinkage) ⁇ V P of the monomer 1 according to the invention from Example 1 (Example 5, B1) was measured by means of density measurement before and after the polymerization and with the commercially available reference monomer 1,10-decanediol dimethacrylate (D 3 MA, CAS: 6701-13-9) (Example 5: Comparative Example V1). D 3 MA was used as a reference because it also has an alkylene spacer between the polymerizable groups and the same atomic distance as 1 .
- the already known (see: U.S. 5,145,374 ) Cyclopolymerizable monomer 2 from Example 2 is used as a reference monomer (Example 5: Comparative Example V2).
- the density of the monomers was determined using a 1 ml pycnometer, while the density of the cured polymers was determined using the Archimedes method.
- the monomers were mixed with 1 mol% BMDG (bis (4-methoxybenzoyl) diethylgermanium) as photoinitiator, poured into a silicone mold (15 x 10 x 4 mm) and exposed to a light oven (model Lumamat 100, Ivoclar AG, 400-500 nm , 20 mW cm -2 ) hardened for 10 minutes per side.
- BMDG bis (4-methoxybenzoyl) diethylgermanium
- the formulations B1, V1 and V2 produced from Example 5 were measured with a real-time near infrared (RT-NIR) photorheometer MCR302 WESP from Anton Paar, which was coupled to a Bruker Vertex-80-IR spectrometer to monitor the turnover.
- R-NIR near infrared
- a PP-25 measuring system was used and the measuring gap was set to 0.2 mm.
- the storage and loss modulus of the samples were measured in the oscillation mode (1% deflection, 1 Hz).
- a base resin formulation (equimolar mixture of the commercially available dimethacrylates urethane dimethacrylate (UDMA, isomer mixture; CAS: 72869-86-4) and 1,10-decanediol dimethacrylate (D 3 MA) was one in each case Component was replaced by an equimolar amount of monomer 1 or reference monomer 2 and the reactivity and shrinkage force were investigated by means of RT-NIR photorheometry.
- UDMA dimethacrylates urethane dimethacrylate
- D 3 MA 1,10-decanediol dimethacrylate
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Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
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EP20155585.1A EP3861976B1 (fr) | 2020-02-05 | 2020-02-05 | Matériaux dentaires à base d'agents de réticulation cyclopolymérisables |
ES20155585T ES2913449T3 (es) | 2020-02-05 | 2020-02-05 | Materiales dentales a base de reticulantes ciclopolimerizables |
CN202110143664.3A CN113288817B (zh) | 2020-02-05 | 2021-02-02 | 基于可环化聚合的交联剂的牙科材料 |
US17/166,003 US11793732B2 (en) | 2020-02-05 | 2021-02-03 | Dental materials based on cyclopolymerizable crosslinkers |
JP2021015477A JP2021123593A (ja) | 2020-02-05 | 2021-02-03 | 環化重合可能なクロスリンカーベースの歯科材料 |
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EP20155585.1A EP3861976B1 (fr) | 2020-02-05 | 2020-02-05 | Matériaux dentaires à base d'agents de réticulation cyclopolymérisables |
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US4889948A (en) * | 1987-08-18 | 1989-12-26 | University Of Southern Mississippi | Acrylate ester ether derivatives |
EP2316407B1 (fr) * | 2009-10-30 | 2021-04-28 | Dentsply DeTrey GmbH | Composition dentaire |
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2020
- 2020-02-05 ES ES20155585T patent/ES2913449T3/es active Active
- 2020-02-05 EP EP20155585.1A patent/EP3861976B1/fr active Active
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- 2021-02-02 CN CN202110143664.3A patent/CN113288817B/zh active Active
- 2021-02-03 JP JP2021015477A patent/JP2021123593A/ja active Pending
- 2021-02-03 US US17/166,003 patent/US11793732B2/en active Active
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US5145374A (en) | 1989-10-03 | 1992-09-08 | The United States Of America As Represented By The Secretary Of Commerce | Synthetic dental compositions formed from cyclopolymerizable bis-acrylate and multi-functional oligomer and bonding method |
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US11793732B2 (en) | 2023-10-24 |
CN113288817B (zh) | 2024-06-14 |
EP3861976B1 (fr) | 2022-03-30 |
JP2021123593A (ja) | 2021-08-30 |
ES2913449T3 (es) | 2022-06-02 |
CN113288817A (zh) | 2021-08-24 |
US20210236388A1 (en) | 2021-08-05 |
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